Tetrahydrofuranylation of Alcohols Using Hypervalent Iodine Reagents

Abstract

Alcohols are converted to their corresponding 2-tetrahydrofuranyl ethers using (diacetoxyiodo)benzene in THF. Reactions are carried out under reflux, or, more effectively, under microwave irradiation. Yields up to 81% are reported without the use of chlorinated solvents.

Key words

hypervalent iodine - bis-THF-ether adduct - oxidations - protecting groups - microwave

References

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Professor Bernhard Witulski, personal communication.

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Microwave Tetrahydrofuranylation . PhI(OAc)₂ (644 mg, 2.0 mmol), THF (2.50 mL) and decanol (0.38 mL, 2.0 mmol) were placed in a microwave tube, with a magnetic stirrer and sealed. The tube was placed in a CEM Discovery Microwave reactor and heated (at 100 W) to 100 °C over 5 min, then maintained at 100 °C for 1 h. Following a 30 min cool time, the tube was removed and the contents purified directly by flash chromatography, using 8:1 petroleum ether-Et₂O. The required fractions were concentrated under reduced pressure to afford a clear, colorless liquid (369 mg, 81%). ¹H NMR (400 MHz, CDCl₃): δ = 0.79 (t, 3 H), 1.10-1.30 (m, 14 H), 1.47 (pent., 2 H), 1.65-1.97 (m, 4 H), 3.28, 3.57, 3.79, 5.03. ¹³C NMR (100MHz, CDCl₃): δ = 14.4, 23.0, 23.9, 26.56, 29.62, 29.68, 29.8, 29.9, 30.1, 32.3, 32.7, 67.0, 67.6, 104.0. MS (EI, 70 eV): m/z (%) = 227 (5) [M - H⁺], 211 (7), 141 (72), 71 (100), 57 (9), 43 (28), 41 (30).
Thermal Tetrahydrofuranylation. PhI(OAc)₂ (322 mg, 1.0 mmol), THF (1.25 mL) and decanol (0.19 mL, 1.0 mmol) were placed in a microwave tube, with a magnetic stirrer and sealed. The tube was placed in an oil bath at 85 °C, for 24 h. The THF was removed under reduced pressure, and the product purified by flash chromatography, using 8:1 petroleum ether-Et₂O (145 mg, 61%).